Work supported by SBU, NSF , NIH, ONR , NSLS

1. Biopolymers-2015 Track 6 Biomaterials and Biopolymers August 11, 2015 14.50-15.10 Structure of Cellulose Nanofibers & its Composite Formation Benjamin Chu1-3 * Departments of Chemistry1, Materials Science & Engineering2, & Biomedical Engineering3 (affiliated member) Stony Brook University, Stony Brook, NY 11794-3400 USA Collaborators from Chu/Hsiao team: Drs. Y. Su, C. Burger, HY Ma, DF Fang, X Wang, and A. Sato (HS student); Professor BS Hsiao Work supported by SBU, NSF, NIH, ONR, NSLS Stony Brook University

2. CHU/HSIAO Research Group Prof. Christian Burger Xiao Wang Dr. Dufei Fang Prof. Ben Hsiao Dr. Hongyang Ma Anna Sato Ying SU Stony Brook University

3. Message for Today 1. (a) Take advantage of most abundant sustainable and renewable materials: Cellulose (crystals) as a basis component. 1. (b) Extraction of Cellulose Nano-fibers & its Characterization 2. (a) Concept 1: Use of Use fibrous format for separation membranes 2. (b) Concept 2: Use nano-fiber/polymer matrix inter-surface as directed water channels for water transport Cellulose Fiber (5 nm) 10 m Fiber 200 nm Fiber Long Island Technology Hall of Fame awarded Patent 8,231,013 B2 “Articles Comprising a Fibrous Support” (by Chu, Hsiao, Yoon): the Long Island Patent of the Year Award in the category of Industrial Innovation on March 6, 2013 – one of 3 from 1500 patents Stony Brook University

4. Plant Hierarchical Structure of Wood Biomass Plant cell Plant cell wall Dr. Ying SU Cellulose molecular chains Cellulose microfibril/nascent crystal Cellulose microfibril aggregate Cellulose fiber Width 10-20 nm Width 3-4 nm Length > 2 μm Width 20-30 μm Length 1-3 mm Figure courtesy of Dr. Christian Burger.

5. Fibrilsurface Dried pulp TEMPO-mediated oxidation1,2, pH=10–11 Extraction of Cellulose Nanofibers from Biomass Cellulose fibril1 Slurry containing oxidized cellulose fibers Centrifugation (2350 g for 10 min) Washing (until pH = 7-8) NaCl NaClO Sonication (79% outpower (60 Hz, 155 W) for 10 min) NaBr NaBrO Centrifugation (4700 g for 30 min) Dialysis (6000–8000 MWCO for 192 hours) Cellulose nanofiber suspension 1 Okita, Saito and A. Isogai, Biomacromolecules, 2010, 11, 1696–1700 2 Ma, Burger, Hsiao, and B. Chu, Biomacromolecules 2011, 12, 970–976

6. Solution SAXS/WAXS of Cellulose Nanofibers Beamline: X9 (NSLS, BNL) Beam wavelength: 0.0885 nm Sample-to-detector distance: SAXS: 3.2 m WAXD: 463 mm Exposure time: 30 s for each measurement, 3 measurements for each sample

7. SAXS Characterization of Cellulose Nano-Fibers New Collimation system Advanced Polymers Beam Line, X27C, National Synchrotron Light Source, Brookhaven National Laboratory, LI, NY Chu, Fang, Mao, Int. J. Mol. Sci. 2015, 16(5), 10016-10037; doi: 10.3390/ijms160510016

8. Data Correction of SAXS/WAXS patterns • Beam center calibration was done using the standard Silver Behenate (d001 = 5.84 nm). • Dead pixels and pixels behind the beam stop were blocked off using dark current and mask correction. • Water scattering together with capillary scattering were subtracted from the suspension scattering. Intensity Averaged measurement of suspension Averaged measurement of water Result after subtraction of water scattering from suspension scattering s (1/nm)

9. Analysis of SAXS Data – Cylinder Model Cotton-1320 Gamma distribution Cotton-7350 Jute Gaussian distribution Biofloc-96 Biofloc-92 0.1 wt% Biofloc-92 Cotton 0.1 wt% R0w = 3.6 ± 2.1 nm Gaussian distribution R0w = 13.8 ± 8.5 nm

10. Analysis of SAXS Data – Ribbon Model 0.6 wt% 0.3 wt% 0.1 wt% Weight-average sizes: aw = 3.2 ± 2.2 nm bw = 9.5 ± 5.0 nm aw+ bw = 12.7 ± 5.5 nm 0.05 wt% Biofloc-96 a + b a b

11. Analysis of SAXS Data – Ribbon Model Cotton-1320 Ribbon model with Gamma distributions of a and b Cotton-7350 Jute Biofloc-96 Biofloc-92 a + b a b

12. Outline 1. Structure of Nanofibrous Membrane Hongyang Ma 2. Microfiltration Membrane 3. Ultrafiltration Membrane Xiao Wang 4. Nanofiltration Membrane Summary Stony Brook University

13. Cellulose Nanofiber Coated Ultrafiltration Membrane 5 m Cellulose Nanofibers E-spun Nanofibers Cellulose Nanofibers E-spun Nanofibers 500 nm SEM images of UCN-based UFmembrane with barrier layer thickness of ~ 100 nm Stony Brook University Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976. Chu, B.; Hsiao, BS.; and Ma HY. WO 2010/042647; PCT/US09/059884.

14. Cross-flow Ultrafiltration of Cellulose Nanofiber-based Membrane for Oil/Water Emulsion Lower rejection ratio Permeation flux of UCN membrane is: 11X higher than that of PAN10 with a comparable rejection ratio, and 2X higher than that of PAN400 with lower rejection ratio Stony Brook University Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976.

15. Ultra-fine Cellulose Nanofiber (UCN) Impregnated Microfiltration Membrane 500 nm Stony Brook University

16. Microfiltration Membranes for Removal of Bacteria, Virusesand Heavy Metal Ions E. Coli 0.5 µm in diameter 2 µm long SARS 100 nm pI = 4.5 As (III), (V) in pesticide and burning coal 2 µm 200 nm B. diminata 0.3 µm in diameter 0.9 µm long Hepatitis A 20-30 nm pI = 3～4 Cr (VI) in dye and paint 2 µm 200 nm Most heavy metal ions have charges and can be interacted via chelating agents Most viruses have pI ＜7, with negative charges at pH = 7 Most bacteria have sizes over 0.2 µm Adsorbed by Charge Interactions & Chelation Adsorbed by Charge Interactions Filtered by Size Exclusion http://www.hyfluxmembranes.com/ http://en.wikipedia.org/wiki/

17. Microfiltration Membrane impregnated with Cellulose Nanofibers E-spun Nanofibers Cellulose Nanofibers Stony Brook University Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2012, 13, 180-186. Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.

18. Cellulose Nanofibers MF Membrame for Removal of E. Coli by Size Exclusion Cross-section view after filtration E. coli was covered on the surface of microfiltration membrane, and the retention was99.9999 %. Top view after filtration Stony Brook University Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.

19. Cellulose Nanofibers MF Membrame for Removal of Virus and Toxic Metal by Adsorption Adsorption capacity of UCN for UO22+ was 167 mg/g; Adsorption capacity of commercially available activited carbon for UO22+ was 57 mg/g. MS2 Adsorption capacity of UCN MF membrane for MS2 was 99%; 10X better than Adsorption capacity of commercially available GS9035 for MS2 which was 90%. UO22+ Ma, HY.; Hsiao, BS.; Chu, B. ACS Macro Lett., 2012, 1, 213-216.

20. Nanofiltration (NF) Membrane Performance as Influenced by Substrates Thin cellulose nanofiber (CN) layer on PAN electro-spun scaffold PSf20 (Sepro), phase-inversioned polysulfone (PSf) Polyacrylonitrile (PAN) electro-spun scaffold Ra: average roughness Rq: root mean squared roughness Rmax: maximum height of the profile

21. Membrane Efficiency Enhanced by Directed Water-Channels PA only PA/CN CN+PA CN only Electro-spun fibers TEM image of NF membrane SEM image of NF membrane Polyamide Introduction of directed water channels In the barrier layer; CN below the resolution of SEM. Cellulose nanofibers * Ma, HY; Burger, C; Hsiao, BS; Chu, B; ACS Macro Lett. 2012, 1, 723−726. Schematic of water-channel structure in composite area *

22. Membrane Performance Further Enhanced by Slot Die coating Membrane Efficiency Enhanced by Slot-Die Coating Steel plate Syringe pump Slot die Track Improvement bipiperidine (BP)

23. E-Spinning & Membranes: Patents and Patent Applications - Chu 2004. 12. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus and Methods for Electrospinning Polymeric Fibers and Membranes,” issued March 30, 2004, Patent #6,713,011; PCT Int. Appl. WO 0292888.   2008. 17. Benjamin Chu, Benjamin S. Hsiao, Michael Hadjiargyrou, Dufei Fang, Steven Zong and Kwangsok Kim, “Cell Delivery System Comprising a Fibrous Matrix and Cells,” issued January 29, 2008, Patent #7,323,190.  18. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Akio Okamoto, “Crosslinking of Hyaluronan Solutions and Nanofibrous Membranes Made Therefrom,” issued January 29, 2008, Patent# 7,323,425. 2010. 20. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Akio Okamoto, “Electro-Blowing Technology for Fabrication of Fibrous Articles and Its Applications of Hyaluronan,” issued February 16, 2010, Patent #7,662,332. 2011. 21. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus for Electro-Blowing or Blowing-Assisted Electro-Spinning Technology and Process for Post Treatment of Electro-spun or Electro-blown Membranes”, US Patent 7,887,311 (2011). 22. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus for Electro-Blowing or Blowing-Assisted Electro-Spinning Technology and Process for Post Treatment of Electro-spun or Electro-blown Membranes”, U.S. Patent 7,934,917 (2011). 2012 23-32. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Kwang-sok Kim, “High Flux and Low Fouling Filtration Media”, U.S. Provisional Patent Application No. 60/616,592, filed October 6, 2004; PCT Int. Appl. WO 2007001405 (2007), AU 2005333585 (issued by Australia), IN 240572 (issued by India, 2011), - - -, U.S. Patent 8,222,166 (2012). 2013 33. Benjamin Chu, Benjamin S. Hsiao and Kyunghwan Yoon “Articles Comprising a Fibrous Support”, filed in SUNY-Stony Brook (R-7925), Docket No. 788-77, U.S. Provisional Application Serial Nos.: 60/872,891 (August 4, 2006) and 60/873,086 (December 06, 2006); or “Articles Comprising a Fibrous Support” U.S. Patent 8,231,013 (2013). Long Island Hall of Fame: Patent of the Year Award in the category of Innovation Industry. Patents & Patent Applications: 34-58 mostly in separation membranes.

24. Condensed Soft Matter Nano(fiber) technology & molecular engineering for environment & health $ $ Thank you for your attention Wuxi Zhongkeguangyuan Biomaterials Co, Ltd Wuxi, China CORPORATION Stony Brook University Shanghai Jieshengyuan Co. Ltd., Shanghai, China